Block Copolymers by Transformation of “Living” Carbocationic into “Living” Radical Polymerization

Coca, Simion; Matyjaszewski, Krzysztof

doi:10.1021/ma970073b

Cited by 151 publications

(87 citation statements)

References 23 publications

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“…For the synthesis of block copolymers containing the first block prepared by ionic mechanism and the second block by radical mechanism, ATRP (atom transfer radical polymerization) processes seem to be best suited, because the functional groups, acting as efficient initiators of ATRP, can be relatively easily introduced as end-groups into polymer chains obtained by ionic mechanism [3][4][5] . It has been shown that ATRP processes are suitable for the controlled polymerization of different groups of monomers, among them acrylates 6) .…”

Section: Introductionmentioning

confidence: 99%

Studies of atom transfer radical polymerization (ATRP) of acrylates by MALDI TOF mass spectrometry

Bednarek

Biedroń

Kubisa³

2000

Macromol. Chem. Phys.

105

125

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Section: Introductionmentioning

confidence: 99%

Studies of atom transfer radical polymerization (ATRP) of acrylates by MALDI TOF mass spectrometry

Bednarek

Biedroń

Kubisa³

2000

Macromol. Chem. Phys.

105

125

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“…In many systems sequential polymerization could be successfully conducted, leading to well defined block copolymers, including block copolymers comprising blocks formed by different polymerization mechanisms 7) . Due to the versatility of ionic ring-opening polymerization, allowing the preparation of polymers with different structures of the main chain, the combination of controlled ionic ring-opening and controlled radical polymerizations is of special interest for the synthesis of novel block copolymers.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of block copolymers by atom transfer radical polymerization oftert-butyl acrylate with poly(oxyethylene) macroinitiators

Bednarek

Biedroń

Kubisa³

1999

Macromol. Rapid Commun.

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SUMMARY: Poly(oxyethylene)s terminated at both ends with 2-bromopropionate end-groups were prepared and characterized by means of MALDI TOF mass spectrometry. It was shown, that atom transfer radical polymerization (ATRP) of methyl methacrylate with a poly(oxyethylene) macroinitiator in bulk proceeds with low initiation efficiency while polymerization of tert-butyl acrylate proceeds with practically quantitative initiation, leading to ABA block copolymers. Originally formed tert-butyl acrylate blocks contain terminal bromine, as expected for the ATRP mechanism. MALDI TOF analysis indicates, however, that in the later stages of polymerization side reactions lead to elimination of terminal bromine.

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“…Several efforts have been devoted to overcome this limitation. Combination of different polymerization techniques, such as cationic polymerization, [9,10] anionic polymerization, [11,12] and condensation polymerizations [13] with CRP is common approach for preparing novel block copolymers constituting with monomers by different mechanisms.…”

Section: Introductionmentioning

confidence: 99%

Zinc powder-alkyl halide: a radical initiation system for living/controlled polymerization of vinyl monomers

Cankaya

Bıçak

2014

Designed Monomers and Polymers

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An initiation system comprising activated zinc powder and alkyl bromide is presented for polymerization of vinyl monomers, including vinyl acetate (VAc). The polymerization was demonstrated to be effected in dry conditions at 70°C and very sensitive to moisture. A radical mechanism was evidenced by spin-trapping method using TEMPO as capping agent and followed block copolymer formation. First order kinetics with respect to concentration of the monomers, methylmethacrylate(MMA), styrene and VAc, relatively long induction periods, and moderate polydispersities (PDI: 1.6-2.4) were determined as typical characteristics of the polymerization system in bulk conditions. The polymerization system was demonstrated to be living, as evidenced by chain extension of the poly (vinyl acetate) (PVAc) with MMA. A ZnBr radical fragment was proposed as key intermediate controlling the chain growth by reversible combination with the active chain ends. The system was also combined with typical copper-mediated atom transfer radical polymerization (ATRP), in which ATRP-growth polystyrene (PS) was directly used as macroinitiator to initiate VAc polymerization yielding block copolymer.

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Block Copolymers by Transformation of “Living” Carbocationic into “Living” Radical Polymerization

Cited by 151 publications

References 23 publications

Studies of atom transfer radical polymerization (ATRP) of acrylates by MALDI TOF mass spectrometry

Studies of atom transfer radical polymerization (ATRP) of acrylates by MALDI TOF mass spectrometry

Synthesis of block copolymers by atom transfer radical polymerization oftert-butyl acrylate with poly(oxyethylene) macroinitiators

Zinc powder-alkyl halide: a radical initiation system for living/controlled polymerization of vinyl monomers

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